José C. S. Costa

Ohmic heating as a new efficient process for organic synthesis in water

A new and efficient process for organic synthesis in aqueous media based on a direct ohmic heating reactor is described. Four representative organic transformations, a Diels–Alder cycloaddition, a nucleophilic substitution, an N-alkylation and a Suzuki cross-coupling reaction, were performed using this process. The results, when compared with those obtained under conventional external heating (oil bath) and microwave heating, showed that ohmic reactor allows faster and more uniform heating and an induced increase of dynamics/mobility of charged species leading in several cases to higher reaction yields and shorter reaction times.

Thermodynamic Insights on the Structure and Energetics of s-Triphenyltriazine

For s-triphenyltriazine, at T = 298.15 K, were measured the standard (p(0) = 10(5) Pa) molar enthalpy of combustion, by static bomb combustion calorimetry, and the standard molar enthalpy, entropy, and Gibbs energy of sublimation by Knudsen/Quartz crystal effusion. A comparison between the entropies of sublimation of s-triphenyltriazine and the isosteric 1,3,5-triphenylbenzene gave a good indication that the higher symmetry of the former contributes significantly to the decrease of its volatility. A computational study at the MP2/cc-pVDZ and B3LYP/6-311++g(d,p) levels of theory was carried out in order to obtain the gas phase geometry, enthalpy, and barriers to internal rotation about the phenyl-triazine bonds. Making use of homodesmotic reaction schemes, a marked stabilization was observed in the molecule of s-triphenyltriazine relative to analogous systems. This result is supported both experimentally and computationally and, combined with a detailed analysis of the literature data concerning the energetics and structure of related compounds, pointed to a significant enthalpic stabilization associated with the exchange of an intramolecular Ar-H···H-Ar close contact by an Ar-H···N(Ar) one. An inspection of the ring-ring torsional profiles in azabenzenes and biphenyls, obtained computationally at the SCS-MP2/cc-pVDZ level, showed that the ring-ring torsions are the dimensions of the potential energy surface (PES) that chiefly determine the energetic differentiation in this class of compounds.

Morphology of Imidazolium‐Based Ionic Liquids as Deposited by Vapor Deposition: Micro‐/Nanodroplets and Thin Films

The morphology of micro- and nanodroplets and thin films of ionic liquids (ILs) prepared through physical vapor deposition is presented. The morphology of droplets deposited on indium-tin-oxide-coated glass is presented for the extended 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cn C1 im][Ntf2 ]; n=1-8) series, and the results show the nanostructuration of ILs. The use of in-vacuum energetic particles enhances/increases the nanodroplets mobility/coalescence mechanisms and can be a pathway to the fabrication of thin IL films.

Energetic and structural study of bisphenols.

We have studied thermochemical, thermophysical and structural properties of bisphenols A, E, F, and AP. In particular, the standard enthalpies of sublimation and the standard enthalpies of formation in the gas phase at 298.15 K for all these species were experimentally determined. A computational study, through M05-2X density functional theory, of the various species shed light on structural effects and further confirmed, by means of the isodesmic reaction scheme, the excellent consistency of the experimental results. Our results reflect also the fact that energetic substituent effects are transferable from diphenylalkanes to bisphenols.

Effect of Self-Association on the Phase Stability of Triphenylamine Derivatives.

The self-association equilibrium, i.e. formation of noncovalent dimers, in two triphenylamine derivatives, TPD (N,N-bis(3-methylphenyl)-N,N-diphenylbenzidine) and mMTDAB (1,3,5-tris[(3-methylphenyl)phenylamino]benzene), in solution was evaluated by (1)H NMR spectroscopy. The gas-phase energetics of the respective dimerization processes was explored by computational quantum chemistry. The results indicate that self-association is significantly more extensive in TPB than in TDAB. It is proposed that this fact helps to explain why TPB presents a stability higher than expected in the liquid phase, which is reflected in a lower melting temperature, a less volatile liquid, and possibly a higher tendency to form a glass. These results highlight the influence of self-association on the phase equilibria and thermodynamic properties of pure organic substances.

Phase Transition Thermodynamics of Bisphenols

Herein we have studied, presented, and analyzed the phase equilibria thermodynamics of a bisphenols (BP-A, BP-E, BP-F, BP-AP, and BP-S) series. In particular, the heat capacities, melting temperatures, and vapor pressures at different temperatures as well as the standard enthalpies, entropies, and Gibbs energies of phase transition (fusion and sublimation) were experimentally determined. Also, we have presented the phase diagrams of each bisphenol derivative and investigated the key parameters related to the thermodynamic stability of the condensed phases. When all the bisphenol derivatives are compared at the same conditions, solids BP-AP and BP-S present lower volatilities (higher Gibbs energy of sublimation) and high melting temperatures due to the higher stability of their solid phases. Solids BP-A and BP-F present similar stabilities, whereas BP-E is more volatile. The introduction of -CH3 groups in BP-F (giving BP-E and BP-A) leads an entropic differentiation in the solid phase, whereas in the isotropic liquids the enthalpic and entropic differentiations are negligible.

3,3'-Bithio-phene.

The title compound, C8H6S2, is disordered [occupancy ratio = 0.839u2005(2):0.161u2005(2)] and sits across a centre of symmetry. In the crystal, the molecules are linked by a weak C—H⋯π interaction.

Thin film deposition of organic hole transporting materials: optical, thermodynamic and morphological properties of naphthyl-substituted benzidines

Aromatic diamines and naphthyl-substituted benzidines (BDB, TPB, TPD, NPB, α-NPD, β-NPB, TNB) are listed as one of the best series available of hole transport materials used as thin films in organic electronics (OLEDs, OPVs). High-quality, homogeneous and compact thin films (≈u2009300xa0nm of thickness) of this compound series were prepared by a physical vapor deposition procedure. SEM and XRD characterizations evidence the amorphous nature of the thin films of NPB, α-NPD, β-NPB and TNB, prepared onto ITO and gold surfaces by a controlling mass flow rate. The semiconducting behavior of this class of π-conjugated materials was investigated through UV–vis characterization by the determination of optical band gaps (≈u20093xa0eV). According to DSC, SEM and XRD analyses, the materials evidenced an amorphous structure and high thermal stability in the glassy state. Analyzing the melting properties, the ratio Tg/Tmu2009=u20092/3 was observed for TPB and NPB, which have a higher molecular symmetry, while Tg/Tmu2009=u20093/4 was observed for the asymmetric β-NPB and TPD. The first accurate measurements of the vapor pressures and thermodynamic properties of phase transition were obtained for the most common hole transport material (NPB) in OLEDs. The relative stability of the crystalline phases of the diamine derivatives (BDB, TPB, NPB) was found to be enthalpically driven, increasing linearly with the molar volume of the compound.